CN108203766A - Rare earth metal metallurgy degassing method - Google Patents
Rare earth metal metallurgy degassing method Download PDFInfo
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- CN108203766A CN108203766A CN201611175185.5A CN201611175185A CN108203766A CN 108203766 A CN108203766 A CN 108203766A CN 201611175185 A CN201611175185 A CN 201611175185A CN 108203766 A CN108203766 A CN 108203766A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/04—Refining by applying a vacuum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/05—Refining by treating with gases, e.g. gas flushing also refining by means of a material generating gas in situ
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Abstract
The present invention provides a kind of rare earth metal metallurgy degassing methods.Rare earth metal metallurgy degassing method includes：Step S1 makes rare earth metal to be purified be melted in vacuum environment, forms molten metal bath；Under the vacuum degree of 0.01~0.05MPa, rare earth hydride is mixed with the molten metal bath by step S2, and keep the temperature 5~30min, degassing molten metal and gaseous state object are obtained, wherein, the rare earth hydride weight is the 0.5~10% of the rare earth metal weight to be purified；The gaseous state object with the degassing molten metal is detached, and the degassing molten metal is cooled down in inert gas, obtains degassing rare earth metal by step S3.Using rare earth hydride, the lower H atom for being detached from the extremely strong reproducibility of generation is combined with elemental gas in molten metal bath near melting temperature, and elemental gas is made to be removed in the form of gaseous compound.The above-mentioned degassing method of the application have the advantages that take it is short, yield is high, low energy consumption.
Description
Technical field
The present invention relates to rare earth metals to refine technical field, in particular to a kind of rare earth metal metallurgy degassing method.
Background technology
Rare earth metal is widely used in high-technology field, and superelevation pure rare-earth metals are research and development new and high technology materials
Critical materials, be the material guarantee for obtaining the functional materials such as high performance magnetic material, luminescent material and energy and material.With height
The development of new technological industry, the demand to high-purity rare earth metal also will be increasingly urgent.
Metal purity has Rare Earth Functional Materials very important meaning：First, high pure metal helps to understand metal
The harm of intrinsic property and impurity to material property；Secondly, the structure sensitive property for illustrating metal material, impurity are helped to defect
The factors such as influence, and thus create conditions to develop the new material design of previously given material character；In addition, contribute to further
The Potential performance of metal, open new application field are disclosed, the extension for high-tech is paved the way.Due to rare earth metal chemistry
Activity is only second to alkali and alkaline earth metal ions element, and reproducibility is close with magnesium, i.e. oxidable in air under room temperature, at high temperature
Negative free energy of formation, the system of rare earth metal can be respectively provided with most metals and nonmetallic effect, the rare earth compound of formation
Standby and purification can only be realized by improving reaction temperature (usual 1000 DEG C or more).It is used to prepare high-purity/superelevation pure rare earth gold
The technology of category mainly includes a variety of methods such as vacuum melting, vacuum distillation, zone refining, electron-beam smelting and Solid State Electrotransport,
It is coupled by technology, realizes the separation of rare earth metal and impurity.But rare earth metal has extremely strong with elemental gas (C, H, O, N etc.)
Binding ability, prepare and purification process in unavoidably introduce gaseous impurity and enter in rare earth metal, form compound and difficult
In removal.In addition, due between the metallic elements such as elemental gas and Fe, Al, Ni electronegativity difference away from big, elemental gas (C,
O, N, S) usually it is mingled in the form of chemical combination there are inside rare earth metal, such as oxide, nitride and sulfide, the type chemical combination
The features such as object fusing point is high, steam forces down and chemical property stablizes, it is difficult to be removed by conventional method.
Rare earth metal is in purification process, and gaseous impurity content is being successively decreased step by step, and many macroscopic properties also can be corresponding
It changes, has especially arrived the deep purifying later stage, the quick reduction of impurity activity can cause purification process mass transfer to be pushed away with reacting
Power reduces, and reduces impurity reaction, diffusive migration rate and the separative efficiency of unit process.It is only capable of at present by simply carrying
Height refining treatment temperature, extension purification time, the increase modes such as purification step and number are miscellaneous to meet gas needed for Purity of Rare Earth
Matter Con trolling index leads to energy consumption cost height, low production efficiency, unstable product quality.
At present, the method for rare earth metal degassing move for solid-state electricity, the melting of hydrogen plasma-arc and outer gettering etc., to depth
Elemental gas in removal metal has preferable effect, but above method production efficiency is extremely low, low output and of high cost, can not
Meet the requirement of mass production, fail to put into actual production.The drawbacks of how overcoming existing rare earth metal method of deoxidation, letter
Elemental gas in easy and economic removal metal is the key technical problem that high pure rare earth metals preparation field needs solve.
Invention content
It is of the prior art dilute to solve it is a primary object of the present invention to provide a kind of rare earth metal metallurgy degassing method
The problem of earth metal purification process period length, low output and high energy consumption.
To achieve these goals, a kind of method according to an aspect of the invention, there is provided rare earth metal metallurgy deaerates,
Including：Step S1 makes rare earth metal to be purified be melted in vacuum environment, forms molten metal bath；Step S2,0.01~
Under the vacuum degree of 0.05MPa, rare earth hydride with the molten metal bath is mixed, and keeps the temperature 5~30min, it is molten to obtain degassing
Melt metal and gaseous state object, wherein, the rare earth hydride weight is the 0.5~10% of the rare earth metal weight to be purified；Step
Rapid S3 detaches the gaseous state object, and the degassing molten metal is cooled down in inert gas with the degassing molten metal,
Obtain degassing rare earth metal.
Further, above-mentioned rare earth metal is La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Lu, Y or Sc.
Further, above-mentioned steps S1 includes：The rare earth metal to be purified is placed in the crucible of intermediate frequency furnace, and
The furnace chamber of the intermediate frequency furnace is vacuumized, forms vacuum chamber；The indifferent gas is filled with into the vacuum chamber
Body is to clean the vacuum chamber, until the vacuum degree of the vacuum chamber is less than 10-2During Pa, by the vacuum chamber into
Row, which is warming up to more than the melting temperature of the rare earth metal to be purified, to be melted the rare earth metal to be purified for 50~100 DEG C, and
The molten metal bath is obtained after 5~15min of heat preservation.
Further, above-mentioned crucible is tungsten crucible.
Further, it is heated up with the power of 10~30kW to the vacuum chamber.
Further, above-mentioned steps S2 includes：Close the evacuating valve of the vacuum system of the intermediate frequency furnace, and to institute
It is 0.01~0.05MPa to state and the inert gas to vacuum degree is filled in vacuum chamber；Rare earth hydride particle is added in institute
It states in molten metal bath, and the temperature of the vacuum chamber to molten metal bath surface is formed into the subsequent continuation of insurance temperature 5 of scull state
~30min obtains degassing molten metal and gaseous state object.
Further, the grain size of above-mentioned rare earth hydride particle is 0.1~5mm.
Further, above-mentioned steps S3 includes：The evacuating valve for opening the vacuum system carries out the vacuum chamber
It vacuumizes；When the vacuum degree of the vacuum chamber is restored to 10-2After below Pa, the vacuum chamber is warming up to described to be purified
More than the melting temperature of rare earth metal 50~300 DEG C, 5~20min is kept the temperature；After heat preservation, the degassing molten metal is poured
It is protected, and is cooled to room temperature using the inert gas after note, obtain the degassing rare earth metal.
Further, above-mentioned inert gas is argon gas.
Further, above-mentioned rare earth hydride is identical with the rare earth element in the rare earth metal to be purified.
It applies the technical scheme of the present invention, rare earth hydride and molten metal bath is mixed, using rare earth hydride molten
Point temperature is lower nearby to be detached from the H atom for generating extremely strong reproducibility, and the hydrogen atom in excitation state oversaturated can dissolve in it is molten
Melt in molten metal, and can be discharged from molten metal, this process that dissolve in-discharges of hydrogen atom can promote reproducibility extremely strong
Hydrogen atom be combined with elemental gas in molten metal bath, make the elemental gas in the compound being mingled in molten metal with gas
The form preservation of compound, such as H2O、CO2、NH3And CH4Deng eventually by volatilization removal.Meanwhile rare earth hydride addition is
0.5~10% (weight) of rare earth metal to be purified not but not causes rare earth metal that hydrogenation occurs, can play instead aobvious
The degasifying effect of work.After the degassing method of the application, without individually using follow-up repeatedly distillation, Solid State Electrotransport or outer suction
The methods of gas method, completes the degassing of rare earth metal depth, obtains the rare earth metal of low-gas content, and this method flow is short, degassing
Significant effect, the secondary pollution that the factors such as purification of metals step length, complex procedures is avoided to bring rare earth metal, reaches low energy
Consumption, the purpose of efficient degassing.The above-mentioned degassing method of the application can be applied to rare earth metal purification melting and vacuum melting rare earth gold
During belonging to target, have that yield is higher, superior product quality.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As recorded in background technology, rare earth metal purification process period of the prior art is long, low output and high energy consumption.
In order to solve this problem, the application one kind typically embodiments, provides a kind of rare earth metal metallurgy deaerate method, including：
Step S1 makes rare earth metal to be purified be melted in vacuum environment, forms molten metal bath；Step S2, in 0.01~0.05MPa
Vacuum degree under, rare earth hydride with molten metal bath is mixed, and keep the temperature 5~30min, obtains degassing molten metal and gaseous state
Object, wherein, rare earth hydride weight is the 0.5~10% of rare earth metal weight to be purified；And step S3, by gaseous state object with taking off
Gas molten metal detaches, and degassing molten metal is cooled down in inert gas, obtains degassing rare earth metal.
The above-mentioned degassing method of the application can be applied to rare earth metal purification melting and vacuum melting rare earth metal target process
In, have that yield is higher, superior product quality.Rare earth hydride and molten metal bath are mixed, using rare earth hydride in fusing point
Temperature is lower nearby to be detached from the H atom for generating extremely strong reproducibility, and the hydrogen atom in excitation state oversaturated can dissolve in melting
It in molten metal, and can be discharged from molten metal, this process that dissolve in-discharges of hydrogen atom can promote reproducibility extremely strong
Hydrogen atom is combined with elemental gas in molten metal bath, and the elemental gas in the compound being mingled in molten metal is made to aerify
Close the form preservation of object, such as H2O、CO2、NH3And CH4Deng eventually by volatilization removal.Meanwhile according to hydride to rare earth metal
Degasifying effect and cost factor, rare earth hydride addition be rare earth metal to be purified 0.5~10% (weight), Ke Yiqi
To significant degasifying effect, and the increase of hydrogen content in rare earth metal will not be caused.After the degassing method of the application, without
The degassing of rare earth metal depth is individually completed using the methods of follow-up repeatedly distillation, Solid State Electrotransport or outer gettering, obtains low gas
The rare earth metal of body content, and this method flow is short, degasifying effect is notable, avoids purification of metals step length, complex procedures etc.
The secondary pollution that factor brings rare earth metal achievees the purpose that low energy consumption, efficient degassing.
The above-mentioned degassing method of the application can be applied in the rare earth metal degassing of current routine, such as each light rare earth,
Middle heavy rare earth, heavy rare earth, the preferably rare earth metal are La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Lu, Y or Sc.
The degassing method of the application can be implemented in intermediate frequency furnace, and then reduce the use cost of this method, and can
The degree of purity of processing environment is improved using the leakproofness of its furnace chamber.It is preferred that when being de-gassed using intermediate frequency furnace, above-mentioned step
Rapid S1 includes：Rare earth metal to be purified is placed in the crucible of intermediate frequency furnace, and the furnace chamber of intermediate frequency furnace take out true
Sky forms vacuum chamber；Inert gas is filled with into vacuum chamber to be cleaned to vacuum chamber, until the vacuum of vacuum chamber
Degree is less than 10-2During Pa, vacuum chamber, which be warming up to, more than the melting temperature of rare earth metal to be purified will wait to carry for 50~100 DEG C
Pure rare-earth metals melt, and obtain molten metal bath after keeping the temperature 5~15min.
The process utilizes vacuum environment, reduces rare earth metal to be purified and causes secondary dirt in fusion process introducing elemental gas
Dye；In addition, metal keeps the temperature 5~15min in the molten state, and extend soaking time under vacuum and be conducive in molten metal
Effumability impurity depth remove；But excessively long heat preservation increases the pollution of crucible impurity in molten metal, thus keeps the temperature
Time is preferably set to 5~15min.
Crucible for intermediate frequency furnace can be the common crucible of current purification of metals, such as tungsten crucible, tantalum crucible etc.,
In order to cost-effective, preferably above-mentioned crucible is tungsten crucible.
In addition, according to characteristics such as the fusing point of rare earth metal, vapour pressures, in order to provide optimum smelting, preferably with 10~30kW
Power heat up to vacuum chamber.
In a kind of preferred embodiment of the application, above-mentioned steps S2 includes：Close the vacuum system of intermediate frequency furnace
Evacuating valve, it is 0.01~0.05MPa that inert gas to vacuum degree is filled with into vacuum chamber；Rare earth hydride particle is added in
Into molten metal bath, and by the temperature of vacuum chamber to molten metal bath surface formed scull state it is subsequent continuation of insurance temperature 5~
30min obtains degassing molten metal and gaseous state object.
Inert gas is filled with into vacuum chamber to increase the indoor pressure of vacuum chamber, and then promotes rare earth hydride to molten
Melt the involvement speed in metal.At a temperature of vacuum chamber, the hydrogen in rare earth hydride is detached from the H originals for generating extremely strong reproducibility
Son, the hydrogen atom in excitation state oversaturated can be dissolved in molten metal, and can be discharged from molten metal, hydrogen it is this
The hydrogen atom that dissolve in-discharging process can promote reproducibility extremely strong is combined with elemental gas in molten metal (C, O, N, S),
It is finally volatilized and removed in the form of gas molecule.
In order to further speed up the hydrogen atom that releases of rare earth hydride, and consider its burn out rate, preferably above-mentioned rare earth hydrogen
The grain size of compound particle is 0.1mm~5mm.
In the application another kind preferred embodiment, above-mentioned steps S3 includes：Open the evacuating valve pair of vacuum system
Vacuum chamber is vacuumized；When the vacuum degree of vacuum chamber is restored to 10-2After below Pa, vacuum chamber is warming up to be purified
More than the melting temperature of rare earth metal 50~300 DEG C, 5~20min is kept the temperature；After heat preservation, after degassing molten metal cast
It is protected, and is cooled to room temperature using inert gas, obtain degassing rare earth metal.
In above-mentioned steps S3, the disengaging effect and metal of consideration degassing object are to the corrosivity of crucible, temperature prioritised control
50~300 DEG C more than melting point metal.After completing to utilize rare earth hydride to the removal of impurities of molten metal, vacuum chamber is carried out
It vacuumizes so that elemental gas (C, O, N, S) combines the gas formed with argon in dedoping step hydrogen atom and molten metal
Gas is extracted, and realizes the separation of degassing molten metal and gaseous state object.Then, degassing melting is realized under the protection of inert gas
The cooling of metal, you can obtain high-purity degassing rare earth metal.
Inert gas employed in above steps is selected from rare gas, in order to reduce spent by inert gas into
This, preferably above-mentioned inert gas is argon gas.
In order to improve the purity of single kind rare earth, the rare earth in preferably above-mentioned rare earth hydride and rare earth metal to be purified
Element is identical.
In a kind of preferred embodiment of the application, above-mentioned degassing method includes：Step S1, in the vacuum of below 0.01Pa
Under the conditions of, heating melts rare earth metal to be purified, forms molten metal bath, and temperature is controlled 50~100 more than melting point metal
DEG C, keep the temperature 5~15min；Step S2 closes pumped vacuum systems, is filled with inert atmosphere to 0.01~0.50MPa, rare earth is hydrogenated
Object is gradually added into molten metal bath, is reduced the critical-temperature that power forms scull to metal surface, and keep the temperature 5~30min, is obtained
To degassing molten metal and gaseous products, wherein, rare earth hydride weight is the 0.5~10% of rare earth metal weight to be purified；
Step S3 reopens pumped vacuum systems, improves power again, and the temperature of metal is increased on fusing point at 50~300 DEG C,
5~20min of heat preservation is carried out, the gaseous products for making cavity and being dissolved in molten metal remove；And step S4：By degassing melting gold
Belong to casting, and cooled down in inert gas, obtain degassing rare earth metal.
Below with reference to embodiment and comparative example, the advantageous effect of the application is further illustrated.
Embodiment 1
2375g rare earth lanthanums to be purified are positioned in the tungsten crucible in intermediate frequency furnace, 119g hydrogenation lanthanums are positioned over
It in feeding chamber, vacuumizes, wherein the grain size of lanthanum hydride particle is 0.1mm~2mm；High-purity argon gas is filled with into vacuum chamber,
After cleaning furnace body 2~3 times, treat that vacuum degree is less than 10-2Pa, starts to heat up with the power of 18kW, and rare earth metal is slowly melted
Change；980 DEG C are continuously heating to after lanthanoid metal all fusing, and keeps the temperature 10min and obtains melting lanthanum liquid；Close vacuum system
Valve, it is 0.03MPa to be filled with high-purity argon gas to vacuum degree；Lanthanum hydride particle in intermediate bunker is added in lanthanum liquid
In, it is 915 DEG C to reduce power to temperature, and keeps the temperature 20min and continue to solution state；Vacuum system evacuating valve is opened, is taken out
Go out the high-purity argon gas and its volatile matter in vacuum chamber, treat that vacuum degree is restored to 10-2After below Pa, power is improved again, it will be golden
The temperature of category is increased at 1150 DEG C, continues to keep the temperature 10min, obtains degassing molten metal；After heat preservation, by degassing melting gold
Belong to after directly pouring into a mould, be filled with high-purity argon gas and protected, and closing intermediate frequency furnace makes degassing molten metal cool to room with the furnace
Temperature obtains high-purity lanthanum rare earth metal of embodiment 1.
Embodiment 2
2306g rare earth lanthanums to be purified are positioned in the tungsten crucible in intermediate frequency furnace, 23g hydrogenation lanthanum particles are placed
It in feeding chamber, vacuumizes, wherein the grain size of hydrogenation lanthanum particle is 1mm~3mm；High-purity argon gas is filled with into vacuum chamber, clearly
After prepurging body 2~3 times, treat that vacuum degree is less than 10-2Pa, starts to heat up with the power of 25kW, and rare earth metal is slowly melted；
1020 DEG C are continuously heating to after lanthanoid metal all fusing, and keeps the temperature 15min and obtains melting lanthanum liquid；Close vacuum system valve
Door, it is 0.03MPa to be filled with high-purity argon gas to vacuum degree；Hydrogenation lanthanum particle in intermediate bunker is added in into lanthanum liquid,
It is 915 DEG C to reduce power to temperature, and keeps the temperature 5min and continue to solution state；Vacuum system evacuating valve is opened, extraction is true
High-purity argon gas and its volatile matter in plenum chamber treat that vacuum degree is restored to 10-2After below Pa, power is improved again, by metal
Temperature is increased at 1200 DEG C, continues to keep the temperature 20min, obtains degassing molten metal；After heat preservation, the molten metal that will deaerate is straight
It after connecing cast, is filled with high-purity argon gas and is protected, and closing intermediate frequency furnace makes degassing molten metal cool to room temperature with the furnace, obtains
Obtain high-purity lanthanum rare earth metal of embodiment 2.
Embodiment 3
2315g rare earth lanthanums to be purified are positioned in the tungsten crucible in intermediate frequency furnace, 46g hydrogenation lanthanum particles are placed
It in feeding chamber, vacuumizes, wherein the grain size of hydrogenation lanthanum particle is 3mm~5mm；High-purity argon gas is filled with into vacuum chamber, clearly
After prepurging body 2~3 times, treat that vacuum degree is less than 10-2Pa, starts to heat up with the power of 10kW, and rare earth metal is slowly melted；
5min is kept the temperature at 970 DEG C obtain melting lanthanum liquid after lanthanoid metal all fusing；Vacuum system valve is closed, is filled with high-purity argon
Gas to vacuum degree is 0.04MPa；Hydrogenation lanthanum particle in intermediate bunker is added in into lanthanum liquid, reduces power to temperature
It is 915 DEG C, and keeps the temperature 30min and continue to solution state；Vacuum system evacuating valve is opened, is extracted out high-purity in vacuum chamber
Argon gas and its volatile matter treat that vacuum degree is restored to 10-2After below Pa, power is improved again, and the temperature of metal is increased to 980 DEG C
Under, continue to keep the temperature 5min, obtain degassing molten metal；After heat preservation, after degassing molten metal is directly poured into a mould, it is filled with high-purity
Argon gas is protected, and closing intermediate frequency furnace makes degassing molten metal cool to room temperature with the furnace, obtains high-purity lanthanum of embodiment 3
Rare earth metal.
Embodiment 4
2301g rare earth lanthanums to be purified are positioned in the tungsten crucible in intermediate frequency furnace, 115g hydrogenation lanthanum particles are put
It is placed in feeding chamber, vacuumizes, wherein the grain size of hydrogenation lanthanum particle is 0.1mm~2mm；High-purity argon is filled with into vacuum chamber
Gas after cleaning furnace body 2~3 times, treats that vacuum degree is less than 10-2Pa starts to heat up with the power of 20kW, by rare earth metal slowly
Fusing；20min is kept the temperature at 1000 DEG C obtain melting lanthanum liquid after lanthanoid metal all fusing；Vacuum system valve is closed, is filled
It is 0.05MPa to enter high-purity argon gas to vacuum degree；Hydrogenation lanthanum particle in intermediate bunker is added in into lanthanum liquid, reduces work(
Rate to temperature is 920 DEG C, and keeps the temperature 20min and continue to solution state；Vacuum system evacuating valve is opened, extracts vacuum chamber out
In high-purity argon gas and its volatile matter, treat that vacuum degree is restored to 10-2After below Pa, power is improved again, by the temperature liter of metal
At up to 1120 DEG C, continue to keep the temperature 10min, obtain degassing molten metal；After heat preservation, degassing molten metal is directly poured into a mould
Afterwards, it is filled with high-purity argon gas to be protected, and closing intermediate frequency furnace makes degassing molten metal cool to room temperature with the furnace, is implemented
High-purity lanthanum rare earth metal of example 4.
Embodiment 5
2320g rare earth lanthanums to be purified are positioned in the tungsten crucible in intermediate frequency furnace, 116g hydrogenation lanthanum particles are put
It is placed in feeding chamber, vacuumizes, wherein the grain size of hydrogenation lanthanum particle is 5.5mm~7mm；High-purity argon is filled with into vacuum chamber
Gas after cleaning furnace body 2~3 times, treats that vacuum degree is less than 10-2Pa starts to heat up with the power of 20kW, by rare earth metal slowly
Fusing；10min is kept the temperature at 950 DEG C obtain melting lanthanum liquid after lanthanoid metal all fusing；Vacuum system valve is closed, is filled with
High-purity argon gas to vacuum degree is 0.05MPa；Hydrogenation lanthanum particle in intermediate bunker is added in into lanthanum liquid, reduces power
It is 915 DEG C to temperature, and keeps the temperature 20min and continue to solution state；Vacuum system evacuating valve is opened, is extracted out in vacuum chamber
High-purity argon gas and its volatile matter, treat that vacuum degree is restored to 10-2After below Pa, power is improved again, and the temperature of metal is increased
To at 1250 DEG C, continue to keep the temperature 25min, obtain degassing molten metal；After heat preservation, degassing molten metal is directly poured into a mould
Afterwards, it is filled with high-purity argon gas to be protected, and closing intermediate frequency furnace makes degassing molten metal cool to room temperature with the furnace, is implemented
High-purity lanthanum rare earth metal of example 5.
Embodiment 6
2190g rare earth lanthanums to be purified are positioned in the tungsten crucible in intermediate frequency furnace, 219g hydrogenation lanthanums are positioned over
It in feeding chamber, vacuumizes, wherein the grain size of lanthanum hydride particle is 0.1mm~2mm；High-purity argon gas is filled with into vacuum chamber,
After cleaning furnace body 2~3 times, treat that vacuum degree is less than 10-2Pa, starts to heat up with the power of 18kW, and rare earth metal is slowly melted
Change；980 DEG C are continuously heating to after lanthanoid metal all fusing, and keeps the temperature 10min and obtains melting lanthanum liquid；Close vacuum system
Valve, it is 0.03MPa to be filled with high-purity argon gas to vacuum degree；Lanthanum hydride particle in intermediate bunker is added in lanthanum liquid
In, it is 915 DEG C to reduce power to temperature, and keeps the temperature 20min and continue to solution state；Vacuum system evacuating valve is opened, is taken out
Go out the high-purity argon gas and its volatile matter in vacuum chamber, treat that vacuum degree is restored to 10-2After below Pa, power is improved again, it will be golden
The temperature of category is increased at 1150 DEG C, continues to keep the temperature 10min, obtains degassing molten metal；After heat preservation, by degassing melting gold
Belong to after directly pouring into a mould, be filled with high-purity argon gas and protected, and closing intermediate frequency furnace makes degassing molten metal cool to room with the furnace
Temperature obtains high-purity lanthanum rare earth metal of embodiment 6.
Embodiment 7
2285g rare earth lanthanums to be purified are positioned in the tungsten crucible in intermediate frequency furnace, 114g hydrogenation lanthanums are positioned over
It in feeding chamber, vacuumizes, wherein the grain size of lanthanum hydride particle is 0.1mm~2mm；High-purity argon gas is filled with into vacuum chamber,
After cleaning furnace body 2~3 times, treat that vacuum degree is less than 10-2Pa, starts to heat up with the power of 18kW, and rare earth metal is slowly melted
Change；980 DEG C are continuously heating to after lanthanoid metal all fusing, and keeps the temperature 10min and obtains melting lanthanum liquid；Close vacuum system
Valve, it is 0.01MPa to be filled with high-purity argon gas to vacuum degree；Lanthanum hydride particle in intermediate bunker is added in lanthanum liquid
In, it is 915 DEG C to reduce power to temperature, and keeps the temperature 20min and continue to solution state；Vacuum system evacuating valve is opened, is taken out
Go out the high-purity argon gas and its volatile matter in vacuum chamber, treat that vacuum degree is restored to 10-2After below Pa, power is improved again, it will be golden
The temperature of category is increased at 1150 DEG C, continues to keep the temperature 10min, obtains degassing molten metal；After heat preservation, by degassing melting gold
Belong to after directly pouring into a mould, be filled with high-purity argon gas and protected, and closing intermediate frequency furnace makes degassing molten metal cool to room with the furnace
Temperature obtains high-purity lanthanum rare earth metal of embodiment 7.
Embodiment 8
2870g rare earth metal holmiums to be purified are positioned in the tungsten crucible in intermediate frequency furnace, 140g hydrogenation holmium particles are put
It is placed in feeding chamber, vacuumizes, wherein the grain size of hydrogenation holmium particle is 0.1mm~2mm；High-purity argon is filled with into vacuum chamber
Gas after cleaning furnace body 2~3 times, treats that vacuum degree is less than 10-2Pa starts to heat up with the power of 20kW, by rare earth metal slowly
Fusing；10min is kept the temperature at 1540 DEG C obtain melting holmium molten metal after metal holmium all fusing；Vacuum system valve is closed, is filled
It is 0.05MPa to enter high-purity argon gas to vacuum degree；Hydrogenation holmium particle in intermediate bunker is added in into holmium metal liquid, reduces work(
Rate to temperature is 1450 DEG C, and keeps the temperature 20min and continue to solution state；Vacuum system evacuating valve is opened, extracts vacuum chamber out
High-purity argon gas and its volatile matter in room treat that vacuum degree is restored to 10-2After below Pa, power is improved again, by the temperature of metal
It is increased at 1600 DEG C, continues to keep the temperature 10min, obtain degassing molten metal；After heat preservation, degassing molten metal is directly poured
It after note, is filled with high-purity argon gas and is protected, and closing intermediate frequency furnace makes degassing molten metal cool to room temperature with the furnace, obtain real
Apply high-purity holmium rare earth metal of example 8.
Embodiment 9
2100g rare earth metal yttriums to be purified are positioned in the tungsten crucible in intermediate frequency furnace, 105g hydrogenation yttrium particles are put
It is placed in feeding chamber, vacuumizes, wherein the grain size of hydrogenation yttrium particle is 0.1mm~2mm；High-purity argon is filled with into vacuum chamber
Gas after cleaning furnace body 2~3 times, treats that vacuum degree is less than 10-2Pa starts to heat up with the power of 20kW, by rare earth metal slowly
Fusing；10min is kept the temperature at 1580 DEG C obtain melting yttrium molten metal after metallic yttrium all fusing；Vacuum system valve is closed, is filled
It is 0.05MPa to enter high-purity argon gas to vacuum degree；Hydrogenation yttrium particle in intermediate bunker is added in into rare earth metal liquid, is reduced
Power to temperature is 1510 DEG C, and keeps the temperature 20min and continue to solution state；Vacuum system evacuating valve is opened, extracts vacuum out
High-purity argon gas and its volatile matter in chamber treat that vacuum degree is restored to 10-2After below Pa, power is improved again, by the temperature of metal
Degree is increased at 1600 DEG C, continues to keep the temperature 10min, obtains degassing molten metal；After heat preservation, the molten metal that will deaerate is direct
It after cast, is filled with high-purity argon gas and is protected, and closing intermediate frequency furnace makes degassing molten metal cool to room temperature with the furnace, obtain
The high-purity yttrium rare earth metal of embodiment 9.
Comparative example 1
2280g rare earth lanthanums to be purified are positioned in the tungsten crucible in intermediate frequency furnace, 114g hydrogenation lanthanum particles are put
It is placed in feeding chamber, vacuumizes, wherein the grain size of hydrogenation lanthanum particle is 0.1mm~2mm；High-purity argon is filled with into vacuum chamber
Gas after cleaning furnace body 2~3 times, treats that vacuum degree is less than 10-2Pa starts to carry out being warming up to 970 DEG C with the power of 20kW, by rare earth
Metal slowly melts；10min is kept the temperature at 980 DEG C obtain melting lanthanum liquid after lanthanoid metal all fusing；Close vacuum system
Valve, it is 0.008MPa to be filled with high-purity argon gas to vacuum degree；Rare earth hydride particle in intermediate bunker is added in rare earth gold
Belong in liquid, it is 915 DEG C to reduce power to temperature, and keeps the temperature 20min and continue to solution state；Open vacuum system extraction valve
Door extracts high-purity argon gas and its volatile matter in vacuum chamber out, treats that vacuum degree is restored to 10-2After below Pa, power is improved again,
The temperature of metal is increased at 1150 DEG C, continues to keep the temperature 10min, obtains degassing molten metal；It is after heat preservation, degassing is molten
After melting metal directly cast, it is filled with high-purity argon gas and is protected, and close intermediate frequency furnace to make degassing molten metal furnace cooling
To room temperature, the high pure rare earth metals of comparative example 1 are obtained.
Comparative example 2
The rare earth lanthanum to be purified prepared after 2310g is restored is positioned in the tungsten crucible in intermediate frequency furnace, 9g hydrogen
Change lanthanum particle to be positioned in feeding chamber, vacuumize, wherein the grain size of hydrogenation lanthanum particle is 0.1mm~2mm；It is filled into vacuum chamber
Enter high-purity argon gas, after cleaning furnace body 2~3 times, treat that vacuum degree is less than 10-2Pa starts to heat up with the power of 20kW, by rare earth
Metal slowly melts；10min is kept the temperature at 980 DEG C obtain melting lanthanum liquid after lanthanoid metal all fusing；Close vacuum system
Valve, it is 0.05MPa to be filled with high-purity argon gas to vacuum degree；Hydrogenation lanthanum particle in intermediate bunker is added in rare earth metal liquid
In, it is 915 DEG C to reduce power to temperature, and keeps the temperature 20min and continue to solution state；Vacuum system evacuating valve is opened, is taken out
Go out the high-purity argon gas and its volatile matter in vacuum chamber, treat that vacuum degree is restored to 10-2After below Pa, power is improved again, it will be golden
The temperature of category is increased at 1130 DEG C, continues to keep the temperature 10min, obtains degassing molten metal；After heat preservation, by degassing melting gold
Belong to after directly pouring into a mould, be filled with high-purity argon gas and protected, and closing intermediate frequency furnace makes degassing molten metal cool to room with the furnace
Temperature obtains the high pure rare earth metals of comparative example 2.
The impurity content of rare earth metal to be purified in embodiment 1 to 9, comparative example 1 and 2 and the rare earth metal that deaerates is carried out
Detection, detection method is pulse-infrared absorption determining Oxygen in Metals nitrogen hydrogen content, carbon and sulphur contents in Means of Electrical Conductivity metal,
Inductively coupled plasma emission spectrography measures W content in metal, and testing result is shown in Table 1 (unit：Weight ppm).
Table 1
It can be seen from the data comparison in 1 embodiment 1 to 5 of table and comparative example 1 and 2 when will use rare earth hydride into
Row degassing, and pass through the dosage for controlling vacuum degree, soaking time and rare earth hydride, the removal efficiency of foreign gas is apparent；Through
The comparison for crossing embodiment 1 and embodiment 4 can be seen that rare earth molten metal process soaking time proper extension, be conducive to impurity
The removal of gas, but the process will also result in the pollution of crucible impurity, therefore, it is not recommended that more than 15min；By embodiment 1
Comparison with embodiment 5 is as can be seen that the particle size of rare earth hydride particle can generate refining effect certain influence, still
For current conventional rare earth hydride granular size, removal effect preferable to foreign gas can be achieved.
It can be seen from the above description that the above embodiments of the present invention realize following technique effect：
The above-mentioned degassing method of the application can be applied to rare earth metal purification melting and vacuum melting rare earth metal target process
In, have that yield is higher, superior product quality.By in rare earth hydride and molten metal bath, using rare earth hydride in fusing point temperature
Degree is lower nearby to be detached from the H atom for generating extremely strong reproducibility, and the hydrogen atom in excitation state oversaturated can dissolve in melting gold
Belong in liquid, and can be discharged from molten metal, this process that dissolve in-discharges of hydrogen atom can promote the extremely strong hydrogen of reproducibility
Atom is combined with elemental gas in molten metal bath, makes the elemental gas in the compound being mingled in molten metal with gas chemical combination
Object, such as H2O、CO2、NH3And CH4Deng eventually by volatilization removal.Meanwhile rare earth hydride addition is rare earth metal to be purified
0.5~10% (weight), not but not hydrogenation and dusting occurs, significant degasifying effect can be played instead.Using this
After the degassing method of application, without individually completing rare earth using the methods of follow-up repeatedly distillation, Solid State Electrotransport or outer gettering
Metal depth degassing process obtains the rare earth metal of low-gas content, and this method flow is short, degasifying effect is notable, avoids gold
Belonging to purification needs the secondary pollution that the links such as long flow path, complex procedures bring rare earth metal, reaches the mesh of low energy consumption high-efficiency degassing
's.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, that is made any repaiies
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
- A kind of method 1. rare earth metal metallurgy deaerates, which is characterized in that including：Step S1 makes rare earth metal to be purified be melted in vacuum environment, forms molten metal bath；Under the vacuum degree of 0.01~0.05MPa, rare earth hydride is mixed with the molten metal bath by step S2, and keeps the temperature 5 ~30min obtains degassing molten metal and gaseous state object, wherein, the rare earth hydride weight is the rare earth metal to be purified The 0.5~10% of weight；Step S3 detaches the gaseous state object, and by the degassing molten metal in inert gas with the degassing molten metal Middle cooling obtains degassing rare earth metal.
- 2. degassing method according to claim 1, which is characterized in that the rare earth metal for La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Lu, Y or Sc.
- 3. degassing method according to claim 1, which is characterized in that the step S1 includes：The rare earth metal to be purified is placed in the crucible of intermediate frequency furnace, and the furnace chamber of the intermediate frequency furnace is taken out Vacuum forms vacuum chamber；The inert gas is filled with into the vacuum chamber to be cleaned to the vacuum chamber, until the vacuum chamber Vacuum degree is less than 10-2During Pa, the vacuum chamber be warming up to more than the melting temperature of the rare earth metal to be purified 50 The rare earth metal to be purified is melted, and obtains the molten metal bath after keeping the temperature 5~15min by~100 DEG C.
- 4. degassing method according to claim 3, which is characterized in that the crucible is tungsten crucible.
- 5. degassing method according to claim 3, which is characterized in that with the power of 10~30kW to the vacuum chamber into Row heating.
- 6. degassing method according to claim 3, which is characterized in that the step S2 includes：The evacuating valve of the vacuum system of the intermediate frequency furnace is closed, and the inert gas is filled with into the vacuum chamber It is 0.01~0.05MPa to vacuum degree；Rare earth hydride particle is added in into the molten metal bath, and by the temperature of the vacuum chamber to molten metal bath Surface forms the subsequent continuation of insurance 5~30min of temperature of scull state, obtains degassing molten metal and gaseous state object.
- 7. degassing method according to claim 6, which is characterized in that the grain size of the rare earth hydride particle for 0.1~ 5mm。
- 8. degassing method according to claim 6, which is characterized in that the step S3 includes：The evacuating valve for opening the vacuum system vacuumizes the vacuum chamber；When the vacuum degree of the vacuum chamber is restored to 10-2After below Pa, the vacuum chamber is warming up to described to be purified dilute More than the melting temperature of earth metal 50~300 DEG C, 5~20min is kept the temperature；After heat preservation, it will be protected, and be cooled to room temperature using the inert gas after the degassing molten metal cast, Obtain the degassing rare earth metal.
- 9. degassing method according to any one of claim 1 to 8, which is characterized in that the inert gas is argon gas.
- 10. degassing method according to any one of claim 1 to 8, which is characterized in that the rare earth hydride and described Rare earth element in rare earth metal to be purified is identical.
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| MYPI2017704771A MY186742A (en) | 2016-12-16 | 2017-12-12 | A method of smelt-degassing of rare earth metals |
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| CN110983076A (en) * | 2019-12-31 | 2020-04-10 | 包头市中鑫安泰磁业有限公司 | Preparation device and preparation method of high-purity rare earth |
| CN112962072A (en) * | 2021-02-02 | 2021-06-15 | 邱从章 | Low-oxygen large-size aluminum-based intermetallic compound-containing alloy target material and preparation method thereof |
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| CN114752814B (en) * | 2022-04-08 | 2023-10-20 | 包头稀土研究院 | Heavy rare earth zinc alloy, method for producing same, use thereof, and use of tungsten-containing container |
| CN114657420B (en) * | 2022-04-08 | 2023-10-20 | 包头稀土研究院 | Light rare earth-zinc alloy, preparation method and application thereof and application of smelting container |
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| CN112962072A (en) * | 2021-02-02 | 2021-06-15 | 邱从章 | Low-oxygen large-size aluminum-based intermetallic compound-containing alloy target material and preparation method thereof |
Also Published As
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| MY186742A (en) | 2021-08-16 |
| JP6491304B2 (en) | 2019-03-27 |
| JP2018095965A (en) | 2018-06-21 |
| CN108203766B (en) | 2019-12-27 |
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Address after: 100088, 2, Xinjie street, Xicheng District, Beijing Patentee after: GRIREM ADVANCED MATERIALS Co.,Ltd. Patentee after: Youyan Technology Group Co.,Ltd. Address before: 100088, 2, Xinjie street, Xicheng District, Beijing Patentee before: GRIREM ADVANCED MATERIALS Co.,Ltd. Patentee before: GENERAL Research Institute FOR NONFERROUS METALS Address after: 100088, 2, Xinjie street, Xicheng District, Beijing Patentee after: GRIREM ADVANCED MATERIALS Co.,Ltd. Patentee after: China Youyan Technology Group Co.,Ltd. Address before: 100088, 2, Xinjie street, Xicheng District, Beijing Patentee before: GRIREM ADVANCED MATERIALS Co.,Ltd. Patentee before: Youyan Technology Group Co.,Ltd. |